J. Org. Chem., Vol. 42, No. 19, 1977 3203
Notes PGEl (sa and 8b). The 1:l mixture of epimeric ester alcohols 7a and 7b (1.15 g, 0.003 26 mol) was dissolved in 15 mL of methanol. An aqueous sodium hydroxide solution [NaOH (150 mg, 0.00375 mol) and 6 mL of HzO] was added to the above solution and the resulting mixture was stirred at room temperature for 20 h. The reaction mixture was poured into 50 mL of Hi0 and extracted with two 50-mL portioas of ether. The aqueous layer was acidified with concentrated HCI at 0 "C and extracted with three 200-mL portions to CH2C12. The dried methylene chloride extracts were concentrated to give 1.0, g (90%)of an oil, crude 8, which solidified on standing at -5 "C. The solid was chromatographed using silica gel G and elution with hexane-ether and ether-CH&lz solutions yielded 800 mg (72%) of a pure 1:l epimeric mixture of 15a- and 15-epi-11deoxy-8-azaPGE1: mp 82.5-85 "C; NMR (CDC13)6 0.87 (t,distorted, 3 H), 1.10-1.90 (br hump), 2.0-2.60 (m) and 2.8-3.70 (m) (24H), 4.28-3.86 (m, 1H), 5.48-5.75 (m, 2 H) and 6.37 (s,2 H). After addition of D20 the resonance peak at 6 6.37 disappeared: IR (KBr) 3400 (shoulder),3200, 2910, 2600 (shoulder),1715 and 1650 cm-'; mass spectrum m/e 339 (M), 322 (M - OH), 321 (M - HzO), 268 (M CsHll), 264 [M - H2O ,end (CH&CH3], 250 (M - CjHll and HzO), 238 (M - Cr,HiiCHOH), 225 [M - CHZ=CH(CH~)~CO~H], 224 [M - (CHz)jCOzH],212 (M - CH=CHCHOHCSH11), 210 [M (CHz)&02H)I. O *67.22; : H, 9.80; N, 4.13. Found: C, Anal. Calcd for C I ~ H [ ~ ~ NC, 67.08; H, 9.91; N, 4.08.
Acknowledgment. We would like to thank the A. H. Robins Co. for a grant in support of this work, Mr. John Forehand for mass spectra data, Mr. Malcolm Stone for microanalysis, and Mr. Ashby F. Johnson, Jr., for coordinating the data obtained from the Robins Co. Registry No.-I, 14-9-87-1;2, 62842-02-8;2 methiodide, 6286145-4; 3 isomer 1, 62861-46-5; 3 isomer 2, 62842-03-9; 4 isomer 1, 62861-47-6;4 isomer 2,62861-48-7; 5,57740-57-5; 6,57740-58-6; 7a, 57740-59-7; 7b, 57740-60-0; 8a, 57740-61-1; ab, 57740-62-2; 2amino-2-methylpropanol, 124-68-5; methyl 7-bromoheptanoate, 54049-24-0;dimethyl (2-oxoheptyl)phosphonate,36969-89-8. References and Notes (1) Undergraduate Research participant.
(2) G. Bolliger and I. M. Muchowski, Tetrahedron Lett., 293 (1975). (3)J. Bruin, H. DeKoning, and H. 0. Huisman, Tetrahedron Lett., 4599 (1975). (4)J. Himizu, S.Saijo, K. Noguchi, M. Wada, Y. Harigaya, and 0. Takaichi, Japan Kakai 76 01, 461;Chem. Abstr., 85, 123751h (1976). (5)For a review of oxazoline chemistry see: J. A. Frump, Chem. Rev., 71,483 (1971);and A. I. Meyers, "Heterocycles in Organic Synthesis", Wiley, New York, N.Y., 1974. (6)I. C. Nordin, J. Heterocycl. Chem., 3,531 (1966). (7)We would like to thank Dr. W. J. Welstead, Jr., and Dr. C. Lunsford of the A. H. Robins Pharmacoutical Company, Richmond, Va., for making these results known to us.
Use of Insoluble Polymer S u p p o r t s i n O r g a n i c Synthesis. 9. Synthesis of Unsymmetrical Carotenoids o n Solid Phases' Clifford C. Leznoff* and Wolodymyr Sywanyk Department of Chemistry, York University, Downsview, Ontario, Canada, M3J l P 3 Received February 16,1977 Carotenoids have been synthesized by many routes.2 One of the most attractive routes to symmetrical carotenoids, such as @-carotene,is the C15 Clo C15 approach? whereby 2 mol of a suitable C15 Wittig reagent reacts with the symmetrical Clo dialdehyde, 2,7-dimethyl-2,4,6-octatrien-1,8-dial( lh4This approach has also been used in the synthesis of unsymmetrical carotenoids such as y-carotene, whereby the symmetrical dialdehyde 1 first reacts with one C15 Wittig reagent to yield the product from reaction at just one end of the aldehyde, namely an a p o ~ a r o t e n a l . ~All , ~ !these ~ cases give apocarotenals or their analogues
